JP3269828B2 - Xylene isomerization catalyst and xylene isomerization reaction method - Google Patents
Xylene isomerization catalyst and xylene isomerization reaction methodInfo
- Publication number
- JP3269828B2 JP3269828B2 JP14786491A JP14786491A JP3269828B2 JP 3269828 B2 JP3269828 B2 JP 3269828B2 JP 14786491 A JP14786491 A JP 14786491A JP 14786491 A JP14786491 A JP 14786491A JP 3269828 B2 JP3269828 B2 JP 3269828B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- xylene
- reaction
- iron
- crystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【０００１】[0001]
【産業上の利用分野】本発明はエチルベンゼンを含有す
るキシレン類の異性化触媒及びキシレン類の異性化反応
方法に関する。The present invention relates to a catalyst for isomerizing xylenes containing ethylbenzene and a method for isomerizing xylenes.
【０００２】[0002]
【従来の技術】周知のように重質ナフサの接触改質、ナ
フサの熱分解、石炭の乾留等で製造されるキシレン類
は、エチルベンゼン、パラキシレン、メタキシレン、オ
ルソキシレンの混合物として産出する。これらのうち需
要はパラキシレンが特に多く、キシレン類より吸着法や
結晶化法でパラキシレンを分離した後、他のキシレン類
をパラキシレンに異性化する必要が生じる。キシレン異
性化触媒は１９５５年世界で始めてイギリスのＩＣＩ社
により工業化され以来、３０年以上の研究の歴史があ
る。初期には水蒸気雰囲気下でシリカ・アルミナ系の固
体酸触媒を用いた。その後水蒸気流中で反応を行ない、
触媒寿命が著しく改善された。触媒は主にシリカ・アル
ミナが用いられたが、白金の有無により、エチルベンゼ
ンの転化が異なり、白金のある場合には、エチルベンゼ
ンはキシレンに異性化される。さらにＭｏｂｉｌ社はＺ
ＳＭ−５と呼ばれる新規なゼオライトの発明を背景に、
特公昭５３−４１６５８に見られるように、それまでの
エチルベンゼンを異性化する方法ではなくて、エチルベ
ンゼンの脱エチル反応によるベンゼン製造という新しい
脱エチル型異性化触媒を開発し始めた。2. Description of the Related Art As is well known, xylenes produced by catalytic reforming of heavy naphtha, pyrolysis of naphtha, carbonization of coal, etc. are produced as a mixture of ethylbenzene, para-xylene, meta-xylene and ortho-xylene. Of these, para-xylene is particularly popular, and it is necessary to separate para-xylene from xylenes by an adsorption method or a crystallization method and then to isomerize other xylenes to para-xylene. The xylene isomerization catalyst has more than 30 years of research history since it was first commercialized in 1955 by ICI, UK. Initially, a silica-alumina solid acid catalyst was used in a steam atmosphere. After that, the reaction is carried out in a steam flow,
The catalyst life was significantly improved. Silica-alumina was mainly used as a catalyst, but the conversion of ethylbenzene differs depending on the presence or absence of platinum. When platinum is present, ethylbenzene is isomerized to xylene. Mobil is also Z
Against the background of the invention of a new zeolite called SM-5,
As can be seen in JP-B-53-41658, a new deethylation type isomerization catalyst has been developed which is not a method of isomerizing ethylbenzene but a benzene production by deethylation reaction of ethylbenzene.
【０００３】[0003]
【発明が解決しようとする課題】脱エチル型異性化触媒
によるキシレン類の異性化反応に含まれる問題点として
は、副反応の抑制がある。即ち、副反応としては大別し
て、キシレン類の水素化分解反応と不均化反応がある。
水素化分解反応は、固体酸触媒を使用する場合、高温程
起こり易くパラフィン、オレフィン、ナフテンを生成し
てキシレン類の損失が生じる。A problem involved in the isomerization reaction of xylenes with a deethylation-type isomerization catalyst is suppression of side reactions. That is, the side reactions are roughly classified into a hydrogenolysis reaction of xylenes and a disproportionation reaction.
In the case of using a solid acid catalyst, the hydrocracking reaction is more likely to occur at higher temperatures, producing paraffins, olefins, and naphthenes, resulting in loss of xylenes.
【０００４】一方、不均化反応はキシレン類間で反応し
てトルエンまたはベンゼンとＣ９芳香族またはＣ10芳香
族が生成する反応であり、同じく固体酸触媒を使用する
場合、高温程起こり易く、原料キシレン類から製造され
るパラキシレン量が少なくなるという問題を生じる。従
って、低温で異性化反応及び脱エチル反応のみ選択性良
く、促進する触媒が求められる。On the other hand, the disproportionation reaction is a reaction in which xylenes are reacted to form toluene or benzene with a C9 aromatic or C10 aromatic. Similarly, when a solid acid catalyst is used, it tends to occur at higher temperatures, There is a problem that the amount of para-xylene produced from xylenes is reduced. Therefore, a catalyst that promotes only isomerization reaction and deethylation reaction at low temperature with good selectivity is required.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、これらの
問題を解決すべく鋭意研究を重ねた結果、４００℃以下
の低温において異性化反応及び脱エチル反応のみ選択性
良く促進する触媒を開発するに至ったものである。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, have found a catalyst which promotes only isomerization reaction and deethylation reaction at a low temperature of 400 ° C. or less with good selectivity. It has been developed.
【０００６】即ち、本発明に係るキシレン異性化触媒
は、結晶性アルミノシリケートのアルミニウムおよび／
またはシリコンの一部が鉄で置換された結晶物である結
晶性鉄アルミノシリケートを担体とし、それに白金を担
持したことを特徴とする。That is, the xylene isomerization catalyst according to the present invention comprises a crystalline aluminosilicate of aluminum and / or
Alternatively, the present invention is characterized in that a crystalline iron aluminosilicate which is a crystal in which a part of silicon is substituted by iron is used as a carrier, and platinum is supported on the carrier.
【０００７】また、本発明に係るキシレン類の異性化反
応方法は、結晶性アルミノシリケートのアルミニウムお
よび／またはシリコンの一部が鉄で置換された結晶物で
ある結晶性鉄アルミノシリケートを担体とし、それに白
金を担持した触媒を用いてキシレン類の異性化反応を行
うに際し、温度を３５０℃〜４００℃の範囲とすること
を特徴とする。Further, the method for isomerizing xylenes according to the present invention comprises the steps of: using a crystalline iron aluminosilicate, which is a crystalline product in which aluminum and / or silicon of the crystalline aluminosilicate is partially substituted with iron, When the xylene isomerization reaction is carried out using a catalyst supporting platinum thereon, the temperature is in the range of 350 ° C to 400 ° C.
【０００８】本発明に係る触媒の担体には結晶性鉄アル
ミノシリケートが用いられる。ここでいう結晶性鉄アル
ミノシリケートは粉末Χ線回折法においてＺＳＭ−５に
代表されるペンタシル型ゼオライトと同一ないし類似の
パターンを示す結晶物を意味し、結晶性アルミノシリケ
ートのアルミニウムおよび／またはシリコンの一部を鉄
で置換した結晶物を意味する。[0008] Crystalline iron aluminosilicate is used as the carrier of the catalyst according to the present invention. The crystalline iron aluminosilicate as referred to herein means a crystal having the same or similar pattern as a pentasil-type zeolite represented by ZSM-5 in powder X-ray diffraction, and includes aluminum and / or silicon of the crystalline aluminosilicate. It means a crystal in which a part is replaced with iron.
【０００９】結晶性鉄アルミノシリケートにおいては触
媒担体の組成比、即ちＳｉＯ2 ／Ｆｅ2 Ｏ3 及びＳｉＯ
2 ／Ａｌ2 Ｏ3 のモル比により、反応生成物の組成が変
わる。例えば結晶性アルミノシリケートの場合、ＳｉＯ
2 ／Ａｌ2 Ｏ3 モル比により担体酸性度が変わるため、
反応生成物の組成が変わる。ＳｉＯ2 ／Ａｌ2 Ｏ3 モル
比が高いとカルボニウムイオン機構による酸性触媒作用
は低下する。即ち、分解反応による軽質パラフィンの減
少、不均化反応による重質芳香族分の減少が起きる。し
かし逆に酸性触媒機能が低下すると異性化反応や脱エチ
ル反応速度も低下する。また酸性度の低いほうがコーク
生成は少なく触媒寿命は長くなる。よって、これらを考
慮し、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比は、５０〜１０００
が好ましく、より好適には１００〜６００である。In the case of crystalline iron aluminosilicate, the composition ratio of the catalyst carrier, ie, SiO 2 / Fe 2 O 3 and SiO 2
The composition of the reaction product changes depending on the molar ratio of 2 / Al 2 O 3 . For example, in the case of crystalline aluminosilicate, SiO 2
Since the carrier acidity changes depending on the 2 / Al 2 O 3 molar ratio,
The composition of the reaction product changes. When the SiO 2 / Al 2 O 3 molar ratio is high, the acidic catalysis by the carbonium ion mechanism decreases. That is, the light paraffin is reduced by the decomposition reaction, and the heavy aromatic component is reduced by the disproportionation reaction. However, conversely, when the acidic catalytic function decreases, the isomerization reaction and the deethylation reaction rate also decrease. Also, the lower the acidity, the less coke is produced, and the longer the catalyst life. Therefore, in consideration of these, the molar ratio of SiO 2 / Al 2 O 3 is 50 to 1000.
Is more preferable, and more preferably 100 to 600.
【００１０】結晶性アルミノシリケートのアルミニウム
および／またはシリコンの一部を鉄で置換すると、酸性
度が変化するとともに、より好ましい性質として、副反
応の不均化反応や水素化分解反応が著しく抑制される。
さらにはキシレン異性化能も改善され、パラキシレン
が、熱力学的平衡値以上に生成する。このように触媒性
能が改善される理由は明白ではないが、結晶内で生成す
るプレンステッド酸点がアルミニウムの近傍にある場合
と鉄の近傍にある場合とではアルミニウムイオンと鉄イ
オンの大きさや電気陰性度の違いから酸強度が変わるこ
とも理由の１つと推定される。また、イオンの大きさの
違いは物理的に結晶内細孔の大きさ、形状を変えると推
定される。鉄イオンの性質は、酸性度や結晶内細孔の大
きさも含め、本反応により適するものと考えられる。鉄
イオンの含有量はＳｉＯ2 ／Ｆｅ2Ｏ3 モル比で２５〜
１０００、より好適には５０〜２００である。When a part of the aluminum and / or silicon of the crystalline aluminosilicate is replaced with iron, the acidity changes, and more preferably, the disproportionation reaction of side reaction and the hydrogenolysis reaction are remarkably suppressed. You.
Furthermore, the xylene isomerization ability is also improved, and para-xylene is generated above the thermodynamic equilibrium value. It is not clear why the catalyst performance is improved in this way, but the size and electric power of aluminum ions and iron ions are different depending on whether the Prensted acid sites generated in the crystal are near aluminum or near iron. It is presumed that one of the reasons is that the acid strength changes due to the difference in negativity. Further, it is presumed that the difference in ion size physically changes the size and shape of the pores in the crystal. The nature of the iron ions, including the acidity and the size of the pores in the crystal, is considered to be more suitable for this reaction. The content of iron ions 25 at SiO 2 / Fe 2 O 3 molar ratio
1000, more preferably 50 to 200.
【００１１】これらの結晶性鉄アルミノシリケートを単
独に異性化用触媒として用いた場合、比較例に示すよう
に不均化反応が多く、エチルベンゼンおよびキシレンの
反応によりベンゼン、トルエン、Ｃ９芳香族、Ｃ１０芳
香族が生成してキシレンの損失が大きい。またエチルベ
ンゼンの脱エチル反応は十分でなく、不均化反応が多
い。When these crystalline iron aluminosilicates are used alone as a catalyst for isomerization, many disproportionation reactions occur as shown in Comparative Examples, and benzene, toluene, C9 aromatic, C10 The generation of aromatics causes a large loss of xylene. In addition, the deethylation reaction of ethylbenzene is not sufficient, and there are many disproportionation reactions.
【００１２】これらの結晶性鉄アルミノシリケートに水
素化能を持つ白金を担持すると、不均化活性を抑制し、
かつエチルベンゼンの異性化反応および脱エチル反応を
起こすことが可能となる。なお従来の触媒系である白金
担持結晶性アルミノシリケートの場合、脱エチル活性は
高く、エチルベンゼン転化率は高く、ベンゼン収率も高
いが、依然としてキシレンの不均化活性も高いため、ト
ルエンとＣ９芳香族収率が高く、キシレンの損失が大き
い。水素化能が高すぎると、水素化反応や水素分解反応
によりキシレン類の損失が増える傾向があるので、周期
率表第ＶＩＩＩ族金属の中でも適度な水素化能を持つ白
金が特に好適となる。担持量は０．０１ないし１．０ｗ
ｔ％で、とくに好適な範囲として０．０５ないし０．５
ｗｔ％である。When platinum having hydrogenation ability is supported on these crystalline iron aluminosilicates, disproportionation activity is suppressed,
In addition, it is possible to cause isomerization reaction and deethylation reaction of ethylbenzene. In the case of a platinum-supported crystalline aluminosilicate, which is a conventional catalyst system, the activity of deethylation is high, the conversion of ethylbenzene is high, and the yield of benzene is high. High family yield and high xylene loss. If the hydrogenation ability is too high, the loss of xylenes tends to increase due to the hydrogenation reaction or the hydrogen decomposition reaction, and therefore, platinum having an appropriate hydrogenation ability is particularly preferable among the Group VIII metals of the periodic table. Loading amount is 0.01 to 1.0w
t%, particularly preferably 0.05 to 0.5
wt%.
【００１３】結晶性鉄アルミノシリケートの合成はいろ
いろな方法があるが、例えば、触媒誌２３巻第３号２３
２ページ（１９８１年）記載のZMS-5 を合成する方法と
同一の方法で実施できる。この方法では、テンプレート
と呼ばれるアルキルアンモニウム塩は、テトラプロピル
アンモニウムブロミドであるが、他に１級ないし３級ア
ミンも使用可能で、同一の結晶構造の結晶性鉄アルミノ
シリケートが合成できる。またこれらの結晶性鉄アルミ
ノシリケートの合成には第８回世界触媒会議予稿集、第
３巻、５６９ページに示される迅速結晶化方法により、
時間を縮めて実施することも可能である。白金を担持さ
せる方法としては、通常のイオン交換法または浸漬法が
用いられる。Although there are various methods for synthesizing crystalline iron aluminosilicate, for example, Catalyst Journal Vol.
It can be carried out by the same method as the method for synthesizing ZMS-5 described on page 2 (1981). In this method, the alkylammonium salt called a template is tetrapropylammonium bromide, but primary to tertiary amines can also be used, and a crystalline iron aluminosilicate having the same crystal structure can be synthesized. In addition, these crystalline iron aluminosilicates were synthesized by the rapid crystallization method shown in the 8th World Catalyst Conference Proceedings, Volume 3, page 569.
It is also possible to reduce the time and carry out. As a method for supporting platinum, a usual ion exchange method or immersion method is used.
【００１４】反応条件は、パラキシレン収率が高く、エ
チルベンゼンが少なくなるような条件できめられる。本
触媒系では３５０℃未満の温度ではキシレンの異性化が
進まず、パラキシレン収率が低く、エチルベンゼンの転
化率も低い。４００℃を越える温度では、キシレン異性
化反応は進むが、それとともに不均化反応が増加してキ
シレン損失が増し、最終的なパラキシレン収率は低下す
る。エチルベンゼンの転化率は温度と共に増加し、それ
に伴いベンゼン収率は増加する。そこで最適温度条件は
生成物の価格変動による経済性の変化とともに若干変化
するが、目的生成物はパラキシレンなので、パラキシレ
ン収率が最大となる３５０℃〜４００℃の範囲が好まし
い。圧力は本反応にはほとんど影響を与えないが、圧力
が高いほど触媒寿命が長くなるので必要な触媒寿命によ
り決められる。また、圧力が高いほど運転コストも上昇
するので、５〜２０Ｋｇ／ｃｍ2 Ｇの範囲が好ましい。
ＬＨＳＶは２〜１０ｈｒ1 、水素比は２〜５ｍｏｌ／ｍ
ｏｌが適当である。The reaction conditions are such that the yield of paraxylene is high and the amount of ethylbenzene is reduced. In the present catalyst system, isomerization of xylene does not proceed at a temperature lower than 350 ° C., the yield of para-xylene is low, and the conversion of ethylbenzene is low. At temperatures above 400 ° C., the xylene isomerization reaction proceeds, but at the same time, the disproportionation reaction increases, the xylene loss increases, and the final para-xylene yield decreases. The conversion of ethylbenzene increases with temperature, and the benzene yield increases accordingly. Therefore, the optimum temperature condition slightly changes with the change in economy due to the price fluctuation of the product, but since the target product is para-xylene, the range of 350 ° C. to 400 ° C. where the para-xylene yield is the maximum is preferable. Although the pressure hardly affects the reaction, the higher the pressure is, the longer the catalyst life is. Therefore, the pressure is determined by the required catalyst life. In addition, the higher the pressure, the higher the operating cost. Therefore, the range of 5 to 20 kg / cm 2 G is preferable.
LHSV is 2 to 10 hr 1 , hydrogen ratio is 2 to 5 mol / m
ol is appropriate.
【００１５】[0015]
【実施例】以下に本発明を実施例によりさらに詳細に説
明するが、本発明の要旨を逸脱しないかぎり、実施例に
限定されるものではない。The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.
【００１６】実施例１ 結晶性鉄アルミノシリケートを次のようにして合成し
た。イオン交換水１８０ｇと硫酸アルミニウム６．５
ｇ、塩化鉄５．４ｇ、硫酸１８．６ｇ、テトラプロピル
アンモニウムブロミド２２．６ｇを混合し、溶液Ａとす
る。イオン交換水１３３ｇと水ガラス（ＪＩＳ３号）２
７０ｇを混合し溶液Ｂとする。イオン交換水３１３ｇと
塩化ナトリウム７．８ｇを混合し、溶液Ｃとする。溶液
ＡおよびＢをそれぞれ滴下ロートに入れ、３０分かけて
激しく攪拌しながら溶液Ｃ中に滴下する。この混合液を
ステンレス製１リットルオートクレーブに入れ、１６０
℃、４８時間反応させる。反応後、生成物を濾別し、濾
液のｐＨが８となるまでイオン交換水で洗浄する。洗浄
後、１１０℃で１６時間乾燥、５３０℃で３時間焼成す
る。焼成後の結晶性鉄アルミノシリケート５０ｇをプロ
トン型にするため１規定塩化アンモニウム水溶液３００
ｍｌ中に浸漬し、８０℃に８時間保った後、同溶液を交
換し、これを４回繰り返す。溶液を濾別後１１０℃で１
６時間乾燥し、５３０℃で３時間焼成する。プロトン化
された結晶性鉄アルミノシンリケート１０ｇをイオン交
換水３０ｍｌ中に浸漬し、その中に、攪拌しながら塩化
白金酸０．１３ｇを溶解した水溶液１０ｍｌを滴下す
る。そのまま約20時間静かに攪拌し、白金塩を結晶性鉄
アルミノシリケート上に十分吸着させた後、蒸発乾固さ
せ、１１０℃で５時間乾燥後、５３０℃、３時間焼成す
る。これを触媒Ａとする。触媒Ａの粉末Ｘ線回折図はＺ
ＳＭ−５と同じであった。触媒ＡのＳｉＯ2／Ｆｅ2 Ｏ3
モル比は１００、ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比は１０
０、白担持量は０．５ｗｔ％である。Example 1 A crystalline iron aluminosilicate was synthesized as follows. 180 g of ion-exchanged water and 6.5 of aluminum sulfate
g, 5.4 g of iron chloride, 18.6 g of sulfuric acid, and 22.6 g of tetrapropylammonium bromide. 133 g of ion exchange water and water glass (JIS No. 3) 2
70 g are mixed to obtain a solution B. 313 g of ion-exchanged water and 7.8 g of sodium chloride are mixed to obtain a solution C. Each of the solutions A and B is placed in a dropping funnel and dropped into the solution C with vigorous stirring over 30 minutes. This mixture was placed in a stainless steel 1 liter autoclave,
Incubate at 48 ° C for 48 hours. After the reaction, the product is separated by filtration and washed with ion-exchanged water until the pH of the filtrate becomes 8. After washing, it is dried at 110 ° C. for 16 hours and baked at 530 ° C. for 3 hours. In order to convert 50 g of the crystalline iron aluminosilicate after calcination into a proton type, a 1N aqueous ammonium chloride solution 300
After immersion in the same solution and keeping at 80 ° C. for 8 hours, the same solution was exchanged, and this was repeated four times. After the solution was filtered off,
Dry for 6 hours and bake at 530 ° C. for 3 hours. 10 g of the protonated crystalline iron aluminosine silicate is immersed in 30 ml of ion-exchanged water, and 10 ml of an aqueous solution in which 0.13 g of chloroplatinic acid is dissolved is added dropwise with stirring. The mixture is gently stirred for about 20 hours, and the platinum salt is sufficiently adsorbed on the crystalline iron aluminosilicate, evaporated to dryness, dried at 110 ° C. for 5 hours, and calcined at 530 ° C. for 3 hours. This is designated as catalyst A. The powder X-ray diffraction pattern of catalyst A is Z
Same as SM-5. SiO 2 / Fe 2 O 3 catalyst A
The molar ratio is 100, and the SiO 2 / Al 2 O 3 molar ratio is 10
0, the amount of supported white is 0.5 wt%.
【００１７】実施例２ 実施例１の溶液Ａ中の硫酸アルミニウムを３．２ｇ、
１．６ｇ、１．１ｇと変えただけで他の操作は全く同様
に実施する。これらをそれぞれ触媒Ｂ、Ｃ、Ｄとする。Example 2 3.2 g of aluminum sulfate in solution A of Example 1
Other operations are performed in exactly the same manner, except that the amounts are changed to 1.6 g and 1.1 g. These are referred to as catalysts B, C, and D, respectively.
【００１８】触媒Ｂ、Ｃ、Ｄは、結晶性鉄アルミノシリ
ケート中のＳｉＯ2 ／Ａｌ2 Ｏ3 モル比が２００、４０
０、６００である。The catalysts B, C and D have a SiO 2 / Al 2 O 3 molar ratio of 200, 40 in the crystalline iron aluminosilicate.
0,600.
【００１９】実施例３ 実験例１の溶液Ａ中の塩化鉄を１．１ｇ、硫酸アルミニ
ウムを１．６ｇと変えただけで他の操作は全く同様に実
施する。これを触媒Ｅとする。触媒ＥのＳｉＯ2 ／Ｆｅ
2 Ｏ3 モル比が５００、ＳｉＯ2／Ａｌ2 Ｏ3 モル比は
４００、白金担持量は０．５ｗｔ％である。Example 3 Other operations were carried out in exactly the same manner as in Experimental Example 1 except that the amount of iron chloride in the solution A was changed to 1.1 g and the amount of aluminum sulfate was changed to 1.6 g. This is designated as catalyst E. SiO 2 / Fe of catalyst E
The molar ratio of 2 O 3 is 500, the molar ratio of SiO 2 / Al 2 O 3 is 400, and the amount of supported platinum is 0.5 wt%.
【００２０】比較例１ 実施例１の白金を担持しない以外、同じ操作を行なった
触媒を触媒ａ１とする。Comparative Example 1 A catalyst prepared in the same manner as in Example 1 except that platinum was not supported was designated as catalyst a1.
【００２１】比較例２ 実施例１で塩化鉄を混合しない以外、同じ操作を行なっ
た触媒を触媒ａ２とする。Comparative Example 2 A catalyst prepared in the same manner as in Example 1 except that iron chloride was not mixed was designated as catalyst a2.
【００２２】実施例４及び比較例３ パラキシレンの少ない異性化用のキシレンを用い、反応
温度３８０℃、圧力８ｋｇ／ｃｍ2 Ｇ、ＬＨＳＶ２．０
ｈｒ1 、水素比３ｍｏｌ／ｍｏｌの条件で反応させた結
果を表１に示す。Example 4 and Comparative Example 3 Using xylene for isomerization with little para-xylene, reaction temperature 380 ° C., pressure 8 kg / cm 2 G, LHSV 2.0
Table 1 shows the results of the reaction under the conditions of hr 1 and a hydrogen ratio of 3 mol / mol.
【００２３】[0023]
【表１】 [Table 1]
【００２４】触媒Ａ、Ｂ、Ｃ、Ｄではエチルベンゼンが
減少してベンゼンが生成し、キシレンの異性化反応も進
むが、キシレンの損失は少ないことが分かる。触媒ａ１
は異性化反応と不均化反応が主反応でキシレンの損失が
大きい。触媒ａ２は不均化反応は減少しているが、パラ
キシレン収率が少ない。In the catalysts A, B, C and D, the amount of ethylbenzene decreases and benzene is produced, and the isomerization reaction of xylene proceeds, but the loss of xylene is small. Catalyst a1
The main reaction is isomerization reaction and disproportionation reaction, and loss of xylene is large. Although the disproportionation reaction of catalyst a2 is reduced, the yield of para-xylene is small.
【００２５】[0025]
【発明の効果】本発明に係る触媒を使用するとキシレン
の不均化反応および水素化分解反応が、おさえられ、キ
シレンのパラキシレンへの異性化反応のみが選択的に進
行する。その結果、従来の触媒に比べ低い反応温度でパ
ラキシレンが高収率で得られる。By using the catalyst according to the present invention, the disproportionation reaction of xylene and the hydrogenolysis reaction are suppressed, and only the isomerization reaction of xylene to para-xylene proceeds selectively. As a result, para-xylene can be obtained in a higher yield at a lower reaction temperature than the conventional catalyst.
【００２６】また、キシレン損失が少ないので、パラキ
シレン分離後の原料を循環することにより、キシレン留
分を有効に利用できる。Since the xylene loss is small, the xylene fraction can be effectively used by circulating the raw material after the para-xylene separation.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 C07B 61/00 300 C07C 5/27 C07C 15/08 ──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int. Cl. 7 , DB name) B01J 21/00-38/74 C07B 61/00 300 C07C 5/27 C07C 15/08
Claims (5)
および／またはシリコンの一部が鉄で置換された結晶物
である結晶性鉄アルミノシリケートを担体とし、それに
白金を担持したことを特徴とするキシレン異性化触媒。1. Xylene isomerization characterized by using a crystalline iron aluminosilicate which is a crystalline product in which a part of aluminum and / or silicon of a crystalline aluminosilicate is substituted by iron as a carrier and carrying platinum thereon. catalyst.
であることを特徴とする請求項１記載のキシレン異性化
触媒。2. The method according to claim 1, wherein the amount of platinum carried is 0.01 to 1.0 wt%.
The xylene isomerization catalyst according to claim 1, wherein
3 モル比２５〜１０００であることを特徴とする請求項
１又は２記載のキシレン異性化触媒。3. The ratio of silica and iron oxide is SiO 2 / Fe 2 O.
The xylene isomerization catalyst according to claim 1 or 2, wherein the molar ratio is 3 to 25 to 1,000.
Ｏ3 モル比５０〜１０００であることを特徴とする請求
項１、２又は３記載のキシレン異性化触媒。4. The method according to claim 1, wherein the ratio of silica to alumina is SiO 2 / Al 2
O 3, characterized in that the molar ratio of 50 to 1000 according to claim 1, wherein the xylene isomerization catalyst.
および／またはシリコンの一部が鉄で置換された結晶物
である結晶性鉄アルミノシリケートを担体とし、それに
白金を担持した触媒を用いてキシレン類の異性化反応を
行うに際し、温度を３５０℃〜４００℃の範囲とするこ
とを特徴とするキシレン類の異性化反応方法。5. Xylene isomers using a crystalline iron aluminosilicate, which is a crystalline product in which aluminum and / or silicon in the crystalline aluminosilicate is partially substituted with iron, and a platinum-supported catalyst. A method for isomerizing xylenes, wherein the temperature is in the range of 350 ° C. to 400 ° C. when performing the isomerization reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14786491A JP3269828B2 (en) | 1991-05-23 | 1991-05-23 | Xylene isomerization catalyst and xylene isomerization reaction method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14786491A JP3269828B2 (en) | 1991-05-23 | 1991-05-23 | Xylene isomerization catalyst and xylene isomerization reaction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04346838A JPH04346838A (en) | 1992-12-02 |
| JP3269828B2 true JP3269828B2 (en) | 2002-04-02 |
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ID=15439975
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14786491A Expired - Fee Related JP3269828B2 (en) | 1991-05-23 | 1991-05-23 | Xylene isomerization catalyst and xylene isomerization reaction method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072128A1 (en) | 2007-12-18 | 2009-06-24 | Tosoh Corporation | Catalyst for reducing nitrogen oxides and process for reducing nitrogen oxides |
| WO2011078149A1 (en) | 2009-12-22 | 2011-06-30 | 東ソー株式会社 | Novel metallosilicate, production method thereof, nitrogen oxide purification catalyst, production method thereof, and nitrogen oxide purification method making use thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101470623B1 (en) | 2006-11-17 | 2014-12-12 | 에스케이이노베이션 주식회사 | Catalyst for xylene isomerization and process for preparing the same |
-
1991
- 1991-05-23 JP JP14786491A patent/JP3269828B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072128A1 (en) | 2007-12-18 | 2009-06-24 | Tosoh Corporation | Catalyst for reducing nitrogen oxides and process for reducing nitrogen oxides |
| US7794680B2 (en) | 2007-12-18 | 2010-09-14 | Tosoh Corporation | Nitrogen oxide-reducing catalyst and method for reducing nitrogen oxide |
| WO2011078149A1 (en) | 2009-12-22 | 2011-06-30 | 東ソー株式会社 | Novel metallosilicate, production method thereof, nitrogen oxide purification catalyst, production method thereof, and nitrogen oxide purification method making use thereof |
| US9675935B2 (en) | 2009-12-22 | 2017-06-13 | Tosoh Corporation | Metallosilicates, processes for producing the same, nitrogen oxide removal catalyst, process for producing the same, and method for removing nitrogen oxide with the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04346838A (en) | 1992-12-02 |
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